DE1165852B - Process for the production of storable thermoplastic polyurethane masses that can be deformed solely by heat and pressure - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 08 g

German class: 39 c - 6

Number: 1 165 852

File number: M 54454 IVd / 39 c

Filing date: October 10, 1962

Opening day: March 19, 1964

Polyurethane elastomers have hitherto generally been made by reacting the components in liquid Stage and prepared by pouring the reaction mixture into molds, in which the mixture is to a crosslinked, rubber-like material. In addition to a higher molecular weight Compound with reactive hydrogen atoms and an organic diisocyanate still Chain extenders used, including the phenylene di - (/ 3-hydroxyethyl ether).

However, since the molding method is not suitable for the production of all kinds of molded articles and, moreover, careful work with each one to avoid air inclusions Requires individual molded part, efforts have already been made to prepare the reaction mixture from all of the above Components in a suitable form e.g. B. to bring on a surface or to pour and the reaction until the reaction mixture solidifies, but not to continue until hardening, but in to interrupt this thermoplastic state. At a later time the preserved can be stored Process polyurethane compound to shape it using heat and pressure alone. However, it is necessary carry out the solidification of the mixture under constant close control and the reaction interrupt at the right time, as the reaction only continues in individual segments the mass leads to considerable defects in the end product and to considerable rejects in the thermoplastic Processing leads, for example, in injection molding or extrusion. Also are the mechanical properties the molded article is uneven when working continuously. After all, because of the necessary If you work carefully, the reaction time until the thermoplastic state is reached is proportionate long.

The invention is an improved process for the production of storable, solely by Thermoplastic polyurethane compositions made from polyhydroxy compounds which can be deformed by heat and pressure a molecular weight of at least 600, diisocyanates and glycols by interrupting the Reaction after sufficient solidification before final crosslinking by cooling.

The process is characterized in that phenylene di - (/ 3-hydroxyethyl ether) is used as the glycol Molar ratio to the polyhydroxyl compound of 0.7 to 7.0 can be used and the ratio of NCO groups of the diisocyanate to the hydroxyl groups in the polyhydroxyl compound and in the Phenylene-di-CjS-hydroxyethyl ether) is 1.04 to 1.14.

Process for the production of storable,
deformable solely by heat and pressure
thermoplastic polyurethane compositions

Applicant:

Mobay Chemical Company, Pittsburgh, Pa.

(V. St. A.)

Representative:

H. Knoblauch, lawyer, Leverkusen

Named as inventor:

James Henry Saunders, New Martinsville, Va.,

Kenneth Allen Pigott, Bridgeville, Pa. (V. St. A.)

Claimed priority:

V. St. v. America October 20, 1961

(146 413)

The use of these glycols in the production of thermoplastic polyurethane compositions makes it possible not only later harder finished products; in particular, the tensile strength is also improved. Important is also the ratio of NCO to OH groups in this context. Will the top If the limit of 1.14 is exceeded (see Comparative Example 2), this is obtained when the polyurethane composition is processed unsatisfactory finished article with defects. If the ratio is below 0.14 (see comparative experiment 1), the solidification time of the poly- urethane mass excessively long. The treatment and especially the crushing of this mass is on Difficult due to its waxy consistency.

The components can be mixed together and the liquid reaction mixture is expedient are spread on a base until the mass solidifies to the thermoplastic intermediate stage. Then the otherwise progressing reaction is interrupted by cooling and the thermoplastic polyurethane mass as such or kept crushed or ground. It can be stored and is among those for thermoplastic Process plastics in the usual conditions using heat and pressure alone. However, the polyhydroxyl compound can also initially be combined with the diisocyanate to form an NCO group Allow the product to pre-react and then add the phenylene di- (jS-hydroxyethyl ether). Ver

409 539/581

3 4

bonds with reactive hydrogen atoms held at about 93 to 260 C. The inside of the form

and a molecular weight of at least 600 are themselves can be kept at 5 to 60 ° C. Of the

especially that for the isocyanate polyaddition molded article can be made in 5 to 200 seconds after injection

known method, containing hydroxyl groups. Then the molding polyester, Polyester amides, polyethers, polythioethers 5 articles are subjected to post-curing, wherein

or polyacetals. You should have a hydroxyl number of er during several hours or even several

have about 25 to 190. The molecular weight will remain for days at elevated temperature,

generally do not exceed 4500. The products of the process are particularly suitable

The preferred molecular weight range is between 1500 for the injection molding of women's shoe heels or

and 3000 and especially at about 2000. io vibration dampers, e.g. B. for engine mounting.

As diisocyanates, the compounds known for isocyanate can also be extruded with high polyaddition processes and strength alone, which can be oriented by curing under or mixed in the stated ratio using tension, with the tensile strength. Diphenylalkane diisocyanate and especially further increased. The elongation of the threads 4,4'-diphenylmethane diisocyanate is also preferred. So- 15 is reduced by the orientation of the threads, probably the o- as well as the m- or p-connections of such fibers and threads are suitable for the phenylene-di- (ß-hydroxyethylether) are as chain clothing industry, especially for Belt or extension device suitable. It is important to have elastic stockings. The thermoplastic, only phenylene-di-fjS-hydroxyäthyläther) to use in the mentioned men- by heat and pressure deformable polyurethane ratio, whereby one can also obtain a small amount of dyes or pigments, amount of one of the usual polyhydric alcohols than whereby one obtains colored molded articles.
Chain extenders can add. To the

However, advantages of the method according to the invention are shown in Example 1

not to be lost, this addition should consist of 10% not 100 parts by weight of a dehydrated polyester

exceed. 25 H moles of ethylene glycol and 10 moles of adipic acid (OH-

Mixing the components together is done number 56; Molecular weight 2000; Acid number 1.5) expediently in the warm at temperatures of 60 are heated to 105 ° C and with each to 105 ° C to 135 ° C. Mixing can be done mechanically preheated 40 parts by weight of 4,4'-diphenylmethane with very short mixing times. The reaction diisocyanate and 19 parts by weight of p-phenylene digemisch are then allowed to react until they solidify, 30 (/ I-hydroxyethyl ether) mixed. The reaction is advantageous at temperatures between 60 and 135 ° C. The mixture, whose NCO to OH ratio is 1.10, is followed in the same way if the polyhydroxyl compound and the chains ^{are first poured onto a base kept at HO 0 C} - where it remains for 12 minutes. During this time it has mixed the agent or if the poly has become sufficiently hard to be removed from the hydroxyl compound, as already described, first. A solid is obtained with which the diisocyanate has been allowed to react. A mold-elastic and thermoplastic polyurethane mass release agent facilitates the removal of the thermoplastic with the following physical properties:
see polyurethane mass from the backing. One tensile strength 457 kg / cm ²

appropriately divides it in time to prevent it from becoming detached _o uau (.on 01

, _TT . ^β ι · ι. τ - «. · ι γ ·· ι_ · Elongation at break 60Ü / ₀

to facilitate from the pad. The storable 40 _OI .,, P. ? , <-, /, "

. , .., ° _n ,., ... _Di -UJ i_ Permanent elongation 35%

thermoplastic polyurethane mass can be passed through <, «worth

Cut, chop and grind as required ^p _{feei] 0} | _{0, De nU} h ng 90 kg / cm ²

and keep for several weeks, if appropriate _{at 2 (χ) 0 /} ; _Deh "";;; _{123 k / cm2}

Cooling even much longer. _{bd 3} '° _De hnung 180 kg / cm ²

The shaping processing of the procedural 45 °

products are made according to the thermoplastic materials used. The material is easy to grind. It can be easy

materials conventionally by injection molding, extrusion, injection molded at 190 ° C in molds for shoe heels

Pressing or the like. The paragraphs obtained are pronounced

When extruding, the material becomes resistant to abrasion at room. In their serial production,

temperature in the feed hopper of the extruder 50 is hardly any waste.

given. In the extruder the temperature of the It is possible to grind waste again and again

Material held at about 93 to 232 ° C. The injection molding.

The degree of compression of the extruder screw can be 3: 1 B 's η' e 1 2
or higher. The screw can be a constant

Have a gear with a variable screw core. 55 The procedure of Example 1 is repeated, extruded molding is z. B. for 12 to 24 hours There are only 33 parts by weight of p-phenylene Hardened 100 to 110 ° C. If that in lumps of di - (/? - hydroxyethyl ether) and 60 parts by weight of 4,4'-Digeschnitzelte When the material is pressed, phenylmethane diisocyanate is used. The reaction should be, the pieces are mixed in a to about 122 to 205 ° C remains on the heated surface for 7 miv preheating given form. There they will take 2 minutes and 60 minutes. It shows the following characteristics:

pressed under high pressure. The mold then has tensile strength of 390 kg / cm ²

cooled to below 122 ° C still under pressure. The elongation at break 525 ° / ₀

Finally, the molded article is removed from the mold. Permanent elongation is 60%

then for 12 to 24 hours at HO ⁰ C off - voltage value

heated. ^: 6 ₅ at 100% elongation 160 kg / cm ²

In the injection molding technique, the cylinder is 203 kg / cm ^{2 at 200% elongation}

Spray device through which the material is poured into the 260 kg / cm ²

Mold interior is conveyed to a temperature Shore hardness D 53

5 6

The material can be converted into fibers at 200.degree. C. The reaction mixture is immediately poured onto one

traditional or at 190 ° C in any form HO ⁰ C heated underlay. In about 12 minutes it is

injection molding. The NCO to OH ratio is 1.1. the mass has become hard and is removed from the base

. -ίο removed and crushed. The mass can be tangy e ι s ρ ι e I 3 _{5 g} j _e ß _{s to} p _ro Dukten with high elasticity and good

At 130 ° C, 100 parts by weight of a poly-physical properties. The reaction mixture

esters from Example 1 with 35 parts by weight of 4,4'-di- has an NCO to OH ratio of 1.04. It can be

phenylmethane diisocyanate mixed. One keeps the easily within economic time limits

Mix to 130 ° C and then cool to work for 30 minutes.

away. After briefly applying a vacuum, comparative experiment 1
16.4 parts by weight of p-phenylene-di- (jS-hydroxyethyl ether)

thoroughly mixed in and the resulting reaction - 100 parts by weight of the polyester from Example 1

mixture on a ^{heated to 110 0} C base are heated to 100 ° C and 40 parts by weight

spread out. The NCO to OH ratio is 1.05. 4,4'-diphenylmethane diisocyanate and 21.1% by weight

Within 12 minutes it solidifies to form a thermo-15 part p-phenylene-di- (/ 9-hydroxyethyl ether) mixed,

plastic polyurethane composition, which is slightly different from the NCO to OH ratio is 1.02. After 30 seconds

The pad is lifted off and by extruding, long mixing, the material is on a HO ⁰ C

Injection molding or pressing can be processed, spread out on which it is up to the heated surface

without a defective surface occurring. Solidification remains. Needed to solidify

. 20 man more than 1 hour; the material is soft and

Example 4 waxy and difficult to remove from the substrate

At 100 ° C, 100 parts by weight of a poly will be lifted and crushed because the particles are in

propylene glycol ethers (molecular weight 2000; OH- of the grinder stick together. During the experiment

Number 56) with 40 parts by weight of 4,4'-diphenylmethane thermoplastic processing is difficult.

diisocyanate and 19 parts by weight of m-phenylene di- 25 in the extruder or in the injection molding machine,

(ß-hydroxyethyl ether), which is also heated to 100 ° C and you get materials of inadequate

have been heated, mixed. You pour the physical properties.

action mixture to a lower tensile strength heated to 110 ° C. 182 kg / cm ²

lay and leave it there for about 15 minutes. Then elongation at break is 540%

the mass is lifted off and the voltage value is reached at room temperature

stores. You can later into fibers with good b _e i 100% elongation 80 kg / cm ²

physical properties extrude. at 200% elongation 98 kg / cm ²

at 300% elongation 123 kg / cm ²

Example5 π ·· ιο

^ Examples.

At 105 ° C., 100 parts by weight of the polyester are used in the procedure of the comparative experiment from Example 1 with 28 parts by weight of toluylene diiso- 20.3 parts by weight ep-phenylene-di - ^ - hydroxyethyl ether) cyanate (mixture of 2,4 and 2,6 isomers [80:20]) and used. The NCO to OH ratio is 1.05. on 19 parts by weight of p-phenylene-di- (/ 3-hydroxyethyl ether), a heated base solidifies the material which were also preheated to 100 ° C, evaporated in about 12 minutes. It is easy to use and mixes. The NCO to OH ratio is 1.1. The reac- to grind. The thermoplastic material can tion mixture is extruded onto a heated base and injection molded. The molds and remains there at 100 ° C until it solidifies. Items show the following physical properties. After about 12 minutes the mass can be shafted:

Lift off the heated surface, shred it and add a tensile strength of 238 kg / cm ²

Fibers with good physical properties ex- elongation at break 580%

pass on. Voltage value

B is ρ ie 1 6 at 100% elongation 80 kg / cm ²

at 200% elongation 98 kg / cm ²

100 parts by weight of polypropylene glycol ether (50 moles at 300% elongation 133 kg / cm ²

gross weight 2000; OH number 56) are mixed with 28 parts by weight of tolylene diisocyanate according to Example 5 and Example 9
19 parts by weight of m-phenylene di - (/? - hydroxyethyl ether) I _n the procedure of the comparative experiment are mixed. All components were previously heated to 100 ° C (18.4 parts by weight of p-phenylene-di-GS-hydroxyethyl ether). The reaction mixture is used at a temperature of 100 ° C. The NCO to OH ratio is 1.12. The heated pad is poured and remains there for about the reaction mixture solidifies on the heated 15 minutes. The solid mass is lifted off and, if supported, within 12 minutes to a mass that is stored at room temperature. It can be easily lifted off and shredded into fibers. Extrude the mass with good physical properties. can be processed thermoplastically to form molded articles,. 60 the virtually no voids in the surface have Example 7 _{and yon au} ß _{eror (} en} tlich high tear strength is.

100 parts by weight of a polyester made from 1,4-butanediol.The mechanical properties are as follows:

and adipic acid (molecular weight 600; acid tensile strength 301 kg / cm ²

number 1.5) are heated to 100 ° C and with 83.3 Ge elongation at break 600%

parts by weight 4,4'-diphenylmethane diisocyanate and 30.7 65 voltage value

Parts by weight of p-phenylene-di- (ß-hydroxyethyl ether), at 100% elongation 77 kg / cm ²

which have also been preheated to 100 ° C, at 200% elongation 100 kg / cm ²

mixed. at 300% elongation 141 kg / cm ²

Comparative experiment 2

In the procedure of comparative experiment 1, 17.4 parts by weight ep-phenylene-di - (^ - hydroxyethyl ether) used. The NCO to OH ratio is 1.16. The material hardens very much on the heated surface quickly to a partially crosslinked material. It is then removed from the backing and carved. It is difficult to process thermoplastically into an article in the desired shape. Extraded Fibers show imperfections on their surface, which are probably due to local crosslinking are due. Articles injection molded from the ground material also show these imperfections. The same applies to processing in press technology. The shelf life of the ground material is very short because the reaction of the reactive components also continues in the solid particles. That Material must therefore - if at all - be processed within a week.

Claims (1)

Claim: Process for the production of storable materials that can be deformed solely by heat and pressure thermoplastic polyurethane compositions from a) polyhydroxyl compounds with a molecular weight of at least 600, b) diisocyanates and c) glycols by interrupting the reaction after sufficient solidification before the final crosslinking by cooling, characterized in that phenylene di - (/? - hydroxyethyl ether) can be used in a molar ratio to a) of 0.7 to 7.0 and the ratio of the NCO groups in b) to the OH groups in a) and c) is 1.04 to 1.14. 409 539/581 3.64 @ Bundesdruckerei Berlin